Accelerator



Patented July 1, 1941 ACCELERATOR Joy G. Lichty, Stow, 'Ohio, assignor to Wingfoot Corporation, Wilmington, Del.,' a corporation of Delaware No Drawing.

Application November'8, 1934, Serial No. 752,123

Q 6 Claims (01. 260793) This invention relates to a new class of compounds the members of which are valuable either as such or with other substances, in the vulcanization of rubber. It relates, among other things, to a method of accelerating the processes of vulcanization by incorporating in the unvulc-anized stock certain chemical compounds which not only are comparatively easy to prepare but also impart desirable physical properties to the vulcanized products; The compounds with which N(diaryl), --N(alkyl) (aryl), etc. In the formula given above, R represents any alkyl group. Where the fatty acid employed is acetic acid, R is methyl; similarly, where butyric acid,

for instance, is employed, R is a propyl group. When the compounds are to be employed as accelerators of vulcanization it will generally be found that it is preferable that the carbonyl group be separated from the dithiocarbamic radical by a single carbon atom. This may be accomplished by employing halogenated fatty acids in which the halogen is attached to the carbon atom alpha to the carbonyl group;

In the type formula, D is more specifically the group In .the latter group, R1 and Ba may be like or imlike radicals or, if desired R1 and R2 may be' taken together to form a cyclic alkylene chain. Also, either R1 or R2, but not both, may be hydrogen.

In general, these compounds" are prepared simply by bringing together solutions of a dithiocarbamate and a halogen-substituted fatty acid. amide. In certain cases, a compound'forms at once; in others, it may be necessary to allow the mixture of the solutions to stand for a few hours or to heat the mixture slightly. 7 In any case, the product forms'as asolid or oil which may be easily separated and purified. The reaction is' found to proceed with substantially equal facility with either a mono or di-halogenate'd fatty amide.

Illustrative of the preparation of these compounds is that of anilino carbonyl methyl di(penta methylene dithiocarbamate). This compound may be prepared by refluxing for a period of 30 minutes a solution of 20.4 grams of dichloro acet anilid and grams of piperidinium' penta methylene dithiocarbamate. A

precipitate is formed which, together withithe.

solvent, is poured into approximately l 'liters of water. The solid,-anilinocarbony1methyl dithiocarbamate, upon being filtered, washed and dried, is obtained in a yield of When further purified by recrystallization from xylene or from a mixture of alcohol and chloroform, it melts with decomposition at 177? C. The equation representing the reaction is as follows:

In the preparation of carbamyl methyl dimethyl dithiocarbamate, an equimolecular mixture of ammonium chloride and mono chloro acet amide in cc. of warm water is added, meanwhile stirring, to 0.4 mol of an aqueous solution of sodium dimethyl dithiocarbamate. The mixture is heated to 45 C., whereupon a solid separates out. The mixture is then cooled to 25 C. and the solid filtered off. Upon washing and drying, 38.7 grams of carbarnyl methyl dimethyl dithiocarbamate melting at 122 C, are obtained. By partial evaporation of the filtrate under reduced pressure, an additional yield of 13 grams of product is obtained. This additional material when recrystallized from alcohol melts at 125 C.

Other compounds of similar nature are carbamyl methyl penta methylene dithiocarbamate, melting at hi l-145 0., and anilino carbonyl methyl pentamethylene dithiocarbamate, melting at 121 C. Still others are ethyl amino carbonyl methyl diethyl dithiocarbamate, amyl amino carbonyl methyl di isoamyl dithiocarbamate, butyl amino carbonyl methyl dibultyl dithiocarbamate, naphthyl amino carbonyl methyl di cyclohexyl dithiocarbamate, benzyl amino carbonyl methyl di(beta phenyl ethylene) dithiocarbamate, morpholyl amino carbonyl methyl ethyl benzyl dithiocarbamate, xylyl amino carbonyl methyl di(hexahydro tolyl) dithiocarbamate, penta methylene amino carbonyl methyl N-methyl tetrahydro alpha furfuryl dithiocarbamate, dimethyl amino carbonyl methyl ethyl dithiocarbamate, and the like.

Dithiocarbamates derived from other amines may be employed in the practice of the invention, examples being those derived from dibutyl amine, methyl cyclohexyl amine, methyl aniline, dibenzyl amine, ditetrahydro furfuryl amine, ethyl cyclohexyl amine, methyl naphthyl amline, diamyl amine and the like. which may be reacted with a solution of any dithiocarbamate are the monoand di-chlor and brom derivatives of acet diphenyl amide, nitro acet anilide, acet toluide, acet phenyl naphthyl These compounds, new in themselves, possess valuable properties as accelerators of vulcanizainstances With the mono halogen derivatives,

Other acet amides.

amide, acet dibutyl amide, acet dicyclohexyl amide, acet ethyl benzyl amide, acet methyl amide, and the like.

The compounds to which the invention relates may be employed as accelerators of vulcanization in substantially any of the standard rubber Stress kgs/cm at- Tensile l Cure tugikexm lIlS, Elongatlon ANILINO CARBONYL METHYL DI PENTA METHYLENE DITHIOGARBAMATE CARBAMYL LIEIHYL PENTA METHYLENE DI'IHIO- SAAAMATE 0.50 PARTDIPHENYLGUANIDINE 0.20

OARBAMYL METHYL DIMETHYL DITHIOOARBAM' ATE 0.50 PART-DIPHENYLGUANIDINE 0.20 PART p on the other hand, activators are in most cases desirable, although not invariably necessary.

It is intended that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty reside in the invention.

What I claim is:

1. The process which comprises vulcanizing a vulcanizablerubber mix in the presence of a compound having the formula wherein D is a thiocarbamyl group and X is an amino group.

2. Theprocess which comprises vulcanizing a vulcanizable rubber mix in the presence of an acetamide in which only one hydrogen atom of the methyl radical attached to the carbonyl group is replaced by the group -S--D, wherein D is a thio carbamyl radical.

3. The process which comprises vulcanizing a vulcanizable rubber mix in the presence of a fattyacid amide in which only one hydrogen atom attached to a carbon atom alpha to the carbonyl group is replaced by the group S-D, wherein D is a thio carbamyl radical.

4. A rubber product which has been vulcanized in the presence of a compound having the formula wherein D is a thio carbamyl group and X is an amino group.

5. A rubber product which has been vulcanized in thepresence of an acetamide in which only one hydrogen atom of the methyl radical attached to the carbonyl group is replaced by the group DS-, wherein D is a thio carbamyl radical.

6. A rubber product which has been vulcanized in the presence of an N-phenyl acetamide in which only one hydrogen atom of the methyl radical attached to the carbonyl group is replaced by the group DS-, wherein D is a thio carbamyl radical.

- JOY G. LICI-ITY. 

